Crystal and Molecular Structures of Two Triazole Derivatives: 4-Cyclopropyl-4,5-dihydro-1H-1,2,3-triazole and Methyl 1-benzyl-1H-1,2,3-triazole-4-carboxylate

Abstract  

The molecule in 4-cyclopropyl-4,5-dihydro-1H-1,2,3-triazole (I) is disposed about a mirror plane with the triazole ring lying in the plane and being orthogonal to the cyclopropyl ring. Considerable delocalization of π-electron density within the triazole ring is indicated by the pattern of bond distances in (I). The molecule of methyl 1-benzyl-1H-1,2,3-triazole-4-carboxylate (II) adopts a curved shape with the dihedral angle formed between the triazole and benzene rings being 63.23(8)°. By contrast to (I), localization of π-electron density within the triazole ring in (II) is indicated. Both (I), via N–H···N hydrogen bonding, and (II), via C–H···O and C–H···N interactions, associate in the solid state to form supramolecular chains. In (I), the chain is a zigzag with a flat topology, whereas in (II) the linear chain has a curved topology. Compound (I) crystallizes in the orthorhombic space group Pnma with a = 5.6470(2) ?, b = 7.3359(4) ?, c = 13.4404(7) ?, and Z = 4. Compound (II) crystallizes in the monoclinic space group P2₁/c with a = 12.1314(5) ?, b = 5.5951(2) ?, c = 16.4339(7) ?, β = 111.269(2)°, and Z = 4.     

Effect of the Random Defects Generated on the Surface of Pt(111) on the Electro-oxidation of Ethanol: An Electrochemical Study

In the present work, the Pt(111) surface was disordered by controlling the density of {110}- and {100}-type defects. The cyclic voltammogram (CV) of a disordered surface in acid media consists of three contributions within the hydrogen adsorption/desorption region: one from the well-ordered Pt(111) symmetry and the other two transformed from the {111}-symmetry with contributions of {110}- and {100}-type surface defects. The ethanol oxidation reaction (EOR) was studied on these disordered surfaces. Electrochemical studies were performed in 0.1 M HClO₄+0.1 M ethanol using cyclic voltammetry and chronoamperometry. Changes in current densities associated to the specific potentials at which each oxidation peak appears suggest that different surface domains of disordered platinum oxidize ethanol independently. Additionally, as the surface-defect density increases, the EOR is catalysed better. This tendency is directly observed from the CV parameters because the onset and peak potentials are shifted to less positive values and accompanied by increases in the oxidation-peak current on disordered surfaces. Similarly, the CO oxidation striping confirmed this same tendency. Chronoamperometric experiments showed two opposite behaviors at short oxidation times (0.1 s). The EOR was quickly catalyzed on the most disordered surface, Pt(111)-16, and was then rapidly deactivated. These results provide fundamental information on the EOR, which contributes to the atomic-level understanding of real catalysts.     

The thermal isomerization of 6-difluoromethylenebicyclo[3.2.0]hept-2-ene

The thermal isomerization of 6-difluoromethylenebicyclo[3.2.0]hept-2-ene proceeds via two competing 1,3-sigmatropic processes, with an E_a nearly identical to that of the hydrocarbon.     

Charge accumulation kinetics in multi-redox molecular catalysts immobilised on TiO2

Multi-redox catalysis requires the accumulation of more than one charge carrier and is crucial for solar energy conversion into fuels and valuable chemicals. In photo(electro)chemical systems, however, the necessary accumulation of multiple, long-lived charges is challenged by recombination with their counterparts. Herein, we investigate charge accumulation in two model multi-redox molecular catalysts for proton and CO₂ reduction attached onto mesoporous TiO₂ electrodes. Transient absorption spectroscopy and spectroelectrochemical techniques have been employed to study the kinetics of photoinduced electron transfer from the TiO₂ to the molecular catalysts in acetonitrile, with triethanolamine as the hole scavenger. At high light intensities, we detect charge accumulation in the millisecond timescale in the form of multi-reduced species. The redox potentials of the catalysts and the capacity of TiO₂ to accumulate electrons play an essential role in the charge accumulation process at the molecular catalyst. Recombination of reduced species with valence band holes in TiO₂ is observed to be faster than microseconds, while electron transfer from multi-reduced species to the conduction band or the electrolyte occurs in the millisecond timescale. Finally, under light irradiation, we show how charge accumulation on the catalyst is regulated as a function of the applied bias and the excitation light intensity.

Using transient spectroelectrochemical techniques, we investigate multiply reduced states of molecular catalysts on titania photoelectrodes as a function of the applied bias and the light intensity.     

Polyelectrolyte condensation induced by linear cations

We examine the role of the condensing agent in the formation of polyelectrolyte bundles, via grand-canonical Monte Carlo simulations. Following recent experiments we use linear, rigid divalent cations of various lengths to induce condensation. Our results clarify and explain the experimental results for short cations. For longer cations we observe novel condensation behavior owing to the alignment of the cations. We also study the role of the polyelectrolyte surface-charge density, and find a nonmonotonic variation in bundle stability. This nonmonotonicity captures two trends that have been observed in separate experiments.     

Thermal elimination of diethyldithiocarbamates and application in the synthesis of (+/-)-ferrugine

Dithiocarbamate-substituted lactams, prepared through group-transfer cyclization reactions of carbamoyl radicals, undergo a Chugaev-like thermal elimination of the dithiocarbamate group in refluxing diphenyl ether to form alpha,beta- and/or beta,gamma-unsaturated amides, depending on the structure of the starting material. This reaction sequence was used to prepare an unsaturated [3.2.2] bridged bicyclic amide, which was converted in a one-pot procedure to the 8-azabicyclo[3.2.1]octane ring system of the tropane alkaloid ferrugine by treatment with phenyllithium followed by aqueous sodium hydroxide.     

Oxidative Crosslinking of Peptides and Proteins: Mechanisms of Formation,Detection, Characterization and Quantification

Covalent crosslinks within or between proteins play a key role in determining the structure and function of proteins. Some of these are formed intentionally by either enzymatic or molecular reactions and are critical to normal physiological function. Others are generated as a consequence of exposure to oxidants (radicals, excited states or two-electron species) and other endogenous or external stimuli, or as a result of the actions of a number of enzymes (e.g., oxidases and peroxidases). Increasing evidence indicates that the accumulation of unwanted crosslinks, as is seen in ageing and multiple pathologies, has adverse effects on biological function. In this article, we review the spectrum of crosslinks, both reducible and non-reducible, currently known to be formed on proteins; the mechanisms of their formation; and experimental approaches to the detection, identification and characterization of these species.     

Study of parameters and entrainment of a jet in cross-flow arrangement with transition at two low Reynolds numbers

Investigation of the mixing process is one of the main issues in chemical engineering and combustion and the configuration of a jet into a cross-flow (JCF) is often employed for this purpose. Experimental data are gained for the symmetry plane in a JCF-arrangement of an air flow using a combination of particle image velocimetry (PIV) with laser-induced fluorescence (LIF). The experimental data with thoroughly measured boundary conditions are complemented with direct numerical simulations, which are based on idealized boundary conditions. Two similar cases are studied with a fixed jet-to-cross-flow velocity ratio of 3.5 and variable cross-flow Reynolds numbers equal to 4,120 and 8,240; in both cases the jet issues from the pipe at laminar conditions. This leads to a laminar-to-turbulent transition, which depends on the Reynolds number and occurs quicker for the case with higher Reynolds number in both experiments and simulations as well. It was found that the Reynolds number only slightly affects the jet trajectory, which in the case with the higher Reynolds number is slightly deeper. It is attributed to the changed boundary layer shape of the cross-flow. Leeward streamlines bend toward the jet and are responsible for the strong entrainment of cross-flow fluid into the jet. Velocity components are compared for the two Reynolds numbers at the leeward side at positions where strongest entrainment is present and a pressure minimum near the jet trajectory is found. The numerical simulations showed that entrainment is higher for the case with the higher Reynolds number. The latter is attributed to the earlier transition in this case. Fluid entrainment of the jet in cross-flow is more than twice stronger than for a similar flow of a jet issuing into a co-flowing stream. This comparison is made along the trajectory of the two jets at a distance of 5.5 jet diameters downstream and is based on the results from the direct numerical simulations and recently published experiments of a straight jet into a co-flow. Mixing is further studied by means of second-order statistics of the passive scalar variance and the Reynolds fluxes. Windward and leeward sides of the jet exhibit different signs for the time-averaged streamwise Reynolds flux 〈v _x ′c′〉. The large coherent structures which contribute to this effect are investigated by means of timely correlated instantaneous PIV-LIF camera snapshots and their contribution to the average statistics of 〈v _x ′c′〉 are discussed. The discussion on mixing capabilities of the jet in cross-flow is supported by simulation results showing the instantaneous three-dimensional coherent structures defined in terms of the pressure fluctuations.